US10059879B2 - Liquid crystal composition, patterned phase delay film and preparation method thereof, and display device - Google Patents

Liquid crystal composition, patterned phase delay film and preparation method thereof, and display device Download PDF

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US10059879B2
US10059879B2 US14/894,798 US201514894798A US10059879B2 US 10059879 B2 US10059879 B2 US 10059879B2 US 201514894798 A US201514894798 A US 201514894798A US 10059879 B2 US10059879 B2 US 10059879B2
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liquid crystal
heat
photo
polymerizable
crystal mixture
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Feifei WANG
Xibin Shao
Dan Wang
Seungmin Lee
Honglin ZHANG
Hebin ZHAO
Ting Dong
Yingying Qu
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BOE Technology Group Co Ltd
Beijing BOE Display Technology Co Ltd
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BOE Technology Group Co Ltd
Beijing BOE Display Technology Co Ltd
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3804—Polymers with mesogenic groups in the main chain
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    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
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    • C09K19/38—Polymers
    • C09K19/3804—Polymers with mesogenic groups in the main chain
    • C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
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    • C09K19/38—Polymers
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    • C09K19/58—Dopants or charge transfer agents
    • C09K19/586—Optically active dopants; chiral dopants
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133382—Heating or cooling of liquid crystal cells other than for activation, e.g. circuits or arrangements for temperature control, stabilisation or uniform distribution over the cell
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1341—Filling or closing of cells
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C09K2019/2042—Ph-Ph-COO-Ph
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C09K2019/2078—Ph-COO-Ph-COO-Ph
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C09K19/322—Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring
    • C09K2019/323—Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring containing a binaphthyl
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    • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
    • C09K2219/03—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used in the form of films, e.g. films after polymerisation of LC precursor
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G02F1/133631—Birefringent elements, e.g. for optical compensation with a spatial distribution of the retardation value

Definitions

  • the present invention relates to the field of display technology, and particularly relates to a liquid crystal composition, a patterned phase delay film prepared from the liquid crystal composition and preparation method thereof, and a display device comprising the phase delay film.
  • 3D Technology comprises polarized 3D technology and Shutter Glass (SG) technology (also known as shutter 3D technology).
  • SG Shutter Glass
  • glasses with polarization function in the polarized 3D technology need to be installed in a Liquid Crystal Display (LCD) module, which makes the cost relatively high and becomes the main factor that limits its application.
  • LCD Liquid Crystal Display
  • FPR Film-type Patterned Retarder
  • Conventional FPR preparation processes are relatively complex. First of all, it requires coating with an alignment liquid. After drying, an alignment film having two different rotatory directions distributed at intervals from each other is prepared using polarizing ultraviolet light. Thereafter, a liquid crystal layer is coated on the alignment film, and the effect of the alignment film allows the liquid crystal layer to have different rotatory directions in adjacent lines. Then a FPR film is obtained by polymerization with ultraviolet light.
  • Embodiments of the present invention are directed to the problem that the preparation process of a patterned phase delay film in the prior art is complex, and provide a liquid crystal composition, a patterned phase delay film prepared from the liquid crystal composition and preparation method thereof, and a display device comprising the phase delay film.
  • a liquid crystal composition which comprises a photo-polymerizable liquid crystal mixture and a heat-polymerizable liquid crystal mixture.
  • the photo-polymerizable liquid crystal mixture and the heat-polymerizable liquid crystal mixture have opposite rotatory directions.
  • a mass ratio of the photo-polymerizable liquid crystal mixture to the heat-polymerizable liquid crystal mixture is 1: (0.4-3).
  • the photo-polymerizable liquid crystal mixture comprises a small molecule nematic liquid crystal, a photo-polymerizable monomer, a UV-absorbing dye, a chiral additive and a photoinitiator.
  • the photo-polymerizable liquid crystal mixture comprises 28-69.5% of small molecule nematic liquid crystal, 15-40% of photo-polymerizable monomer, 2-15% of UV-absorbing dye, 0-25% of chiral additive and 0.5-5% of photoinitiator.
  • the photo-polymerizable monomer may either be a photo-polymerizable liquid crystal monomer or a non-liquid crystal photo-polymerizable monomer.
  • the photo-polymerizable liquid crystal monomer may include any one of the following substances:
  • the UV-absorbing dye includes:
  • the photoinitiator includes:
  • the heat-polymerizable liquid crystal mixture comprises a small molecule nematic liquid crystal, a heat-polymerizable monomer, a curing agent and a chiral additive.
  • the heat-polymerizable liquid crystal mixture comprises 35-73% of small molecule nematic liquid crystal, 10-20% of heat-polymerizable monomer, 12-20% of curing agent and 5-25% of chiral additive.
  • the heat-polymerizable monomer includes a bisphenol F epoxy resin having the following molecular formula:
  • the curing agent includes 1,8-diamino-3,6-dioxaoctane having the following molecular formula:
  • the chiral additive includes any one of the following substances:
  • a patterned phase delay film with high reflectance and transmittance can be obtained by UV-polymerizing and heat-polymerizing the liquid crystal composition.
  • the preparation process is simple and the costs are low.
  • a patterned phase delay film which is prepared from the above-mentioned liquid crystal composition.
  • a preparation method for a patterned phase delay film which comprises the following steps: injecting the above mentioned liquid crystal mixture into a liquid crystal cell; irradiating the liquid crystal cell covered with a photo mask with UV light to complete UV-polymerization; and heating the liquid crystal cell to complete heat-polymerization.
  • the condition for the UV-polymerization is wavelength of the UV light being 365 nm, intensity being 0.001-100 mW/cm 2 , and irradiation time being 5-240 min.
  • the condition for the heat-polymerization is temperature ranging from 30 to 120° C. and heating time ranging from 20 to 60 min.
  • a display device which comprises the above mentioned patterned phase delay film.
  • the display device comprises the above mentioned patterned phase delay film, it can be used in 3D display with the advantages of simple preparation, low costs, and the like.
  • FIG. 2 is a schematic diagram of the region formed by UV radiation which reflects laevorotatory visible light band in the first embodiment of the present invention
  • FIG. 3 is a schematic diagram of the region formed by heating which reflects dextrorotatory visible light band in the first embodiment of the present invention.
  • FIG. 4 is a curve diagram of the transmittance of the patterned phase delay film formed in the first embodiment of the present invention in the range of wavelength of 350 nm-750 nm.
  • a liquid crystal composition which comprises a laevorotatory photo-polymerizable liquid crystal mixture and a dextrorotatory heat-polymerizable liquid crystal mixture.
  • the photo-polymerizable liquid crystal mixture and heat-polymerizable liquid crystal mixture may comprise the previously mentioned various specific components. It should be understood that it is also possible to mix any other heat-polymerizable liquid crystal mixture and photo-polymerizable liquid crystal mixture in the prior art, as long as the optically rotatory directions of the two mixtures are opposite.
  • the photo-polymerizable liquid crystal mixture or heat-polymerizable liquid crystal mixture may comprise a small molecule nematic liquid crystal.
  • a liquid crystal temperature of the small molecule nematic liquid crystal ranges from ⁇ 20° C. to 120° C.
  • an optical anisotropy ⁇ n ranges from 0.19 to 0.21 (589 nm, 293K), e.g., SLC1717 (Shijiazhuang Yongshenghuaqing Liquid Crystal LTD.), MAT 10-1614 (Merck Corporation), ZBE-5371XX (JNC Corporation), and the like.
  • a patterned phase delay film which is prepared from the above-mentioned liquid crystal composition.
  • the preparation method comprises the following steps: injecting the above mentioned liquid crystal composition into a liquid crystal cell; irradiating the liquid crystal cell covered partially with a photo mask with UV light to complete the UV-polymerization; and heating the liquid crystal cell to complete the heat-polymerization so as to form the patterned phase delay film.
  • the liquid crystal composition can be obtained by uniformly mixing the photo-polymerizable liquid crystal mixture and heat-polymerizable liquid crystal mixture by means of solvent evaporation or heat melting.
  • solvent evaporation and heat melting are conventional approaches.
  • the solvent is usually selected from organic solvents, such as tetrahydrofuran, acetone, dichloromethane, or the like.
  • the liquid crystal composition can be heated to its clearing point temperature to carry out the melt mixing. The specific operation conditions will not be repeated here.
  • the liquid crystal composition is injected into the liquid crystal cell 2 on the glass substrate 1 , and the photo mask 3 is placed on the liquid crystal cell 2 .
  • the photo mask 3 may be a photo shielding strip arranged at intervals.
  • the liquid crystal cell 2 may be irradiated with UV light at a wavelength of 365 nm, under an irradiation intensity of 0.001-100 mW/cm 2 for 5-240 min. In some embodiments, the irradiation intensity of the UV light is 0.1-15 mW/cm 2 and the irradiation time is 10-100 min.
  • the concentration gradient of the photo-polymerizable monomer may be represented by a polymerization rate difference in the photo-polymerizable monomer polymerization.
  • the polymerization rate is faster at the side near the UV light, which causes the photo-polymerizable monomers away from the UV light and those at the place covered by the photo mask 3 to migrate to the side near the UV light.
  • Most of the photo-polymerizable monomers may migrate to the light permeable region of the photo mask 3 .
  • the polymer network formed near the UV light is more intensive than that formed away from the UV light. That is, in the direction vertical to the polymer network (i.e.
  • the concentration gradient of the polymer network of photo-polymerizable monomers is formed.
  • the photo-polymerizable monomers at the place covered by the photo mask 3 may migrate to the side near the UV light, so the concentration gradient of the polymer network of photo-polymerizable monomers is also formed in the horizontal direction of the liquid crystal cell.
  • the photo-polymerizable liquid crystal monomers at the place of the liquid crystal cell 2 irradiated with the UV light are polymerized during the migration, and after the polymerization, a concentration gradient polymer network of photo-polymerizable monomers is formed at the place of the liquid crystal cell 2 irradiated with the UV light.
  • the rotatory direction of the concentration gradient polymer network may be determined by the contents and optical rotation of the chiral substances in the system. So the system exhibits levorotation if the content of the laevorotatory substance is higher, and the network after polymerization is a laevorotatory network. If the content of the dextrorotatory substance is higher in the system, the system exhibits dextrorotation, and the network after polymerization is a dextrorotatory network.
  • the UV-polymerized liquid crystal cell is placed on a heating platform for heating, so that the heat-polymerizable monomers in the liquid crystal composition are polymerized.
  • the temperature of the heating platform may be 30° C.-120° C., and the heat curing time may be 20-60 min. In some embodiments, the temperature of the heating platform may be 80° C.-100° C., and the heat curing time may be 40-50 min.
  • the polymerization of heat-polymerizable monomers takes place when the temperature reaches the heat initiation temperature. Pure UV light irradiation would not lead to the heat-polymerization.
  • the step of UV light irradiation since the difference of the polymerization rates of the photo-polymerizable monomers may cause the photo-polymerizable monomers to move to the direction with the stronger UV light, a majority of the heat-polymerizable monomers will be passively migrated (in the opposite direction), and the concentration gradient of heat-polymerizable monomers may be also formed.
  • the content of heat-polymerizable monomers is lower near the place where the UV light is stronger, while the content of heat-polymerizable monomers is higher at the place where the UV light is weaker and the place covered by the photo mask 3 , so the most of the heat-polymerizable monomers are migrated to the place covered by the photo mask, and thus the concentration gradient of heat-polymerizable monomers is formed opposite to the concentration gradient of photo-polymerizable monomers. That is, the concentration gradient of heat-polymerizable monomers is also formed in both the horizontal direction and vertical direction of the liquid crystal cell. During the heating, the concentration gradient of the polymer network of heat-polymerizable monomers is also formed in both the horizontal direction and vertical direction of the liquid crystal cell.
  • the system exhibits levorotation if the content of the laevorotatory substance is higher and the network after polymerization is a laevorotatory network, and if the content of the dextrorotatory substance is higher, the system exhibits dextrorotation, and the network after polymerization is a dextrorotatory network.
  • the heat-polymerizable monomers remained at the exposed place of the photo mask (i.e. the irradiated place of the photo mask) are polymerized upon heating. But the heat-polymerizable monomers remained at the exposed place of the photo mask (with lower contents) are not sufficient to change the optical rotation of the polymer network of photo-polymerizable monomers which has higher contents.
  • the heat-polymerizable monomers function to further stabilize the laevorotatory polymer network which is formed previously from the photo-polymerizable monomers.
  • the patterned phase delay film may be finally formed which may reflect laevorotatory polarized light and dextrorotatory polarized light at different positions.
  • the laevorotatory and dextrorotatory polarization states may be separately distributed at intervals in accordance with the shape of the photo mask, that is, linear polarized lights of the same polarization state emitted from the adjacent pixel lines of the display panel may be converted into laevorotatory circular polarized lights and dextrorotatory circular polarized lights respectively.
  • concentration gradients of polymer networks may be formed in the different regions (i.e. the covered region and the exposed region of the mask), i.e., helical pitch gradients of a cholesteric liquid crystal composite system.
  • the helical pitch gradients of the cholesteric liquid crystal composite system correspond to the selective reflection bandwidth range.
  • ⁇ is the selective reflection bandwidth
  • ⁇ n is the liquid crystal birefringence
  • ⁇ p is the helical pitch gradient of the liquid crystal composite system.
  • a patterned phase delay film which may be prepared from the liquid crystal composition according to the embodiments of the present invention by the above-mentioned preparation method.
  • the patterned phase delay film may have the advantages of simple preparation process and low cost.
  • a display device which comprises the above-mentioned patterned phase delay film. Since the display device is configured with the above-mentioned patterned phase delay film, it can be used in 3D display.
  • the present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture.
  • the amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1.
  • the laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 (Shijiazhuang Yongshenghuaqing Liquid Crystal LTD.) as the small molecule nematic liquid crystal, the photo-polymerizable liquid crystal monomer having the molecular formula of:
  • UV-absorbing dye having the molecular formula of:
  • the dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, a bisphenol F epoxy resin as the heat-polymerizable monomers having the following molecular formula:
  • the laevorotatory photo-polymerizable liquid crystal mixture and dextrorotatory heat-polymerizable liquid crystal mixture may be mixed into a uniform mixture according to the mixing mass ratio of Table 1 by means of solvent evaporation, thereby obtaining a liquid crystal composition, wherein the total mass of the photo-polymerizable liquid crystal mixture is 1 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 1 gram.
  • the mass of each component in the photo-polymerizable liquid crystal mixture may be calculated according to the mass percentage in Table 1, and the corresponding mass of each component is weighed.
  • the respective components may be placed into a 5 ml glass bottle. Acetone may be added slowly, dropwise into the glass bottle until the components are completely dissolved.
  • the glass bottle may be placed on a heating platform of 40° C. for 5-6 hours until the solvent evaporates completely, and the formulation of the photo-polymerizable liquid crystal mixture is finished. Then, the heat-polymerizable liquid crystal mixture may be formulated according to the same process.
  • the above-mentioned liquid crystal mixtures may be injected into the liquid crystal cell 2 on the glass substrate 1 , and the photo mask 3 may be placed on the prepared liquid crystal cell 2 .
  • the pattern of the photo mask 3 may be photo shielding strips arranged at intervals.
  • the liquid crystal cell 2 may be irradiated with UV light at a wavelength of 365 nm, under an irradiation intensity of 1.4 mW/cm 2 , for 25 minutes.
  • the polymerization network of the photo-polymerizable monomers may reflect laevorotatory visible light bands, and hence the region on the liquid crystal layer corresponding to the light permeable region of the photo mask 3 may reflect the laevorotatory visible light bands.
  • the UV-polymerized liquid crystal cell is placed on a heating platform (for heating), so that the heat-polymerizable monomers in the liquid crystal mixtures are polymerized.
  • the temperature of the heating platform may be 80° C., and the heat curing time may be 45 minutes.
  • the polymerization network obtained by curing the heat-polymerizable monomers may form a region which may reflect dextrorotatory visible light bands.
  • the patterned phase delay film is finally formed which may reflect the laevorotatory polarized light and dextrorotatory polarized light at different positions.
  • the laevorotatory and dextrorotatory polarization films are separated from each other and distributed at intervals in accordance with the shape of the photo mask, so that the polarization films can convert the linear polarized lights of the same polarization state emitted from the adjacent pixel lines of the display panel into the laevorotatory circular polarized lights and dextrorotatory circular polarized lights respectively.
  • the concentration gradients of the polymer networks are formed at different regions (the covered region and exposed region of the mask), i.e., helical pitch gradients of a cholesteric liquid crystal composite system.
  • Curve 1 is the spectrum curve of the portion obtained by UV-polymerization, which may implement the selective reflection of laevorotatory light in the waveband range of 350 nm-750 nm.
  • Curve 2 is the spectrum curve of the portion obtained by heat-polymerization, which may implement the selective reflection of dextrorotatory light in the waveband range of 350 nm-750 nm.
  • the present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture.
  • the amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1, wherein the total mass of the photo-polymerizable liquid crystal mixture is 1.43 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 0.57 gram.
  • the laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the photo-polymerizable liquid crystal monomers having the molecular formula of:
  • UV-absorbing dye having the molecular formula of:
  • the dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 (Shijiazhuang Yongshenghuaqing Liquid Crystal LTD.) as the small molecule nematic liquid crystal, a bisphenol F epoxy resin as the heat-polymerizable monomer having the following molecular formula:
  • the patterned phase-delay film may be prepared according to the same preparation process as in the first embodiment with the differences that the wavelength of the UV irradiation is 365 nm, the UV light intensity is 100 mW/cm 2 , the duration of UV irradiation is 5 minutes, the temperature of the heating platform is 40° C., and the heat curing time is 50 minutes.
  • the spectrogram of the patterned phase-delay film obtained after the two-step polymerization is similar to FIG. 4 .
  • the present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture.
  • the amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1, wherein the total mass of the photo-polymerizable liquid crystal mixture is 0.67 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 1.33 gram.
  • the laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the photo-polymerizable liquid crystal monomers having the molecular formula of:
  • UV-absorbing dye having the molecular formula of:
  • the dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, a bisphenol F epoxy resin as the heat-polymerizable monomer having the following molecular formula:
  • the patterned phase delay film may be prepared according to the same preparation process as in the first embodiment with the differences that the wavelength of the UV irradiation is 365 nm, the UV light intensity is 30 mW/cm 2 , the duration of UV irradiation is 90 minutes, the temperature of the heating platform is 50° C., and the heat curing time is 40 minutes.
  • the spectrogram of the patterned phase-delay film obtained after the two-step polymerization is similar to FIG. 4 .
  • the present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture.
  • the amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1, wherein the total mass of the photo-polymerizable liquid crystal mixture is 0.5 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 1.5 gram.
  • the laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the photo-polymerizable liquid crystal monomers having the molecular formula of:
  • UV-absorbing dye having the molecular formula of:
  • the dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystals, the polyethylene glycol bisglycidyl ether as the heat-polymerizable monomer having the following molecular formula:
  • 1,8-diamino-3,6-dioxaoctane as the curing agent having the following molecular formula:
  • the patterned phase delay film may be prepared according to the same preparation process as in the first embodiment with the differences that the wavelength of the UV irradiation is 365 nm, the UV light intensity is 60 mW/cm 2 , the duration of UV irradiation is 60 minutes, the temperature of the heating platform is 70° C., and the heat curing time is 35 minutes.
  • the spectrogram of the patterned phase-delay film obtained after the two-step polymerization is similar to FIG. 4 .
  • the present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture.
  • the amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1, wherein the total mass of the photo-polymerizable liquid crystal mixture is 1.11 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 0.89 gram.
  • the laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystals, the photo-polymerizable liquid crystal monomers having the molecular formula of:
  • UV-absorbing dye having the molecular formula of:
  • the dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the polyethylene glycol bisglycidyl ether as the heat-polymerizable monomer having the following molecular formula:
  • 1,8-diamino-3,6-dioxaoctane as the curing agent having the following molecular formula:
  • the patterned phase delay film may be prepared according to the same preparation process as in the first embodiment with the differences that the wavelength of the UV irradiation is 365 nm, the UV light intensity is 0.001 mW/cm 2 , the duration of UV irradiation is 240 minutes, the temperature of the heating platform is 30° C., and the heat curing time is 60 minutes.
  • the spectrogram of the patterned phase-delay film obtained after the the two-step polymerization is similar to FIG. 4 .
  • the present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture.
  • the amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1, wherein the total mass of the photo-polymerizable liquid crystal mixture is 0.57 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 1.43 gram.
  • the laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the photo-polymerizable liquid crystal monomers having the molecular formula of:
  • UV-absorbing dye having the molecular formula of:
  • the dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the polyethylene glycol bisglycidyl ether as the heat-polymerizable monomers having the following molecular formula:
  • 1,8-diamino-3,6-dioxaoctane as the curing agent having the following molecular formula:
  • the patterned phase delay film may be prepared according to the same preparation process as in the first embodiment with the differences that the wavelength of the UV irradiation is 365 nm, the UV light intensity is 80 mW/cm 2 , the duration of UV irradiation is 30 minutes, the temperature of the heating platform is 100° C., and the heat curing time is 25 minutes.
  • the spectrogram of the patterned phase-delay film obtained after the two-step polymerization is similar to FIG. 4 .
  • Table 1 shows the mass ratios of the photo-polymerizable mix liquid crystals and heat-polymerizable mix liquid crystals as well as the mixing ratios in the above embodiments.

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Abstract

A liquid crystal composition comprises a photo-polymerizable liquid crystal mixture and a heat-polymerizable liquid crystal mixture, and the two mixtures have opposite rotatory directions. A patterned phase delay film is prepared from the liquid crystal composition. A display device comprises the phase delay film. The preparation of the patterned phase-delay film can be implemented by a two-step polymerization process including UV-polymerization and heat-polymerization. The process is simple and the costs are low.

Description

TECHNICAL FIELD
The present invention relates to the field of display technology, and particularly relates to a liquid crystal composition, a patterned phase delay film prepared from the liquid crystal composition and preparation method thereof, and a display device comprising the phase delay film.
BACKGROUND
3D Technology comprises polarized 3D technology and Shutter Glass (SG) technology (also known as shutter 3D technology). Currently, glasses with polarization function in the polarized 3D technology need to be installed in a Liquid Crystal Display (LCD) module, which makes the cost relatively high and becomes the main factor that limits its application. However, Film-type Patterned Retarder (FPR) technology developed by LG Display utilizes films as substitutes of the glasses, which allows the costs to be reduced by three quarters and achieves a strong competitiveness in price.
Conventional FPR preparation processes are relatively complex. First of all, it requires coating with an alignment liquid. After drying, an alignment film having two different rotatory directions distributed at intervals from each other is prepared using polarizing ultraviolet light. Thereafter, a liquid crystal layer is coated on the alignment film, and the effect of the alignment film allows the liquid crystal layer to have different rotatory directions in adjacent lines. Then a FPR film is obtained by polymerization with ultraviolet light.
SUMMARY
Embodiments of the present invention are directed to the problem that the preparation process of a patterned phase delay film in the prior art is complex, and provide a liquid crystal composition, a patterned phase delay film prepared from the liquid crystal composition and preparation method thereof, and a display device comprising the phase delay film.
According to one aspect of the present invention, there is provided a liquid crystal composition which comprises a photo-polymerizable liquid crystal mixture and a heat-polymerizable liquid crystal mixture. The photo-polymerizable liquid crystal mixture and the heat-polymerizable liquid crystal mixture have opposite rotatory directions.
In an embodiment, a mass ratio of the photo-polymerizable liquid crystal mixture to the heat-polymerizable liquid crystal mixture is 1: (0.4-3).
In an embodiment, the photo-polymerizable liquid crystal mixture comprises a small molecule nematic liquid crystal, a photo-polymerizable monomer, a UV-absorbing dye, a chiral additive and a photoinitiator.
In an embodiment, assume that total mass of the photo-polymerizable liquid crystal mixture is 100%, the photo-polymerizable liquid crystal mixture comprises 28-69.5% of small molecule nematic liquid crystal, 15-40% of photo-polymerizable monomer, 2-15% of UV-absorbing dye, 0-25% of chiral additive and 0.5-5% of photoinitiator.
The photo-polymerizable monomer may either be a photo-polymerizable liquid crystal monomer or a non-liquid crystal photo-polymerizable monomer. In an embodiment, the photo-polymerizable liquid crystal monomer may include any one of the following substances:
Figure US10059879-20180828-C00001
In an embodiment, the UV-absorbing dye includes:
Figure US10059879-20180828-C00002
In an embodiment, the photoinitiator includes:
Figure US10059879-20180828-C00003
In an embodiment, the heat-polymerizable liquid crystal mixture comprises a small molecule nematic liquid crystal, a heat-polymerizable monomer, a curing agent and a chiral additive.
In an embodiment, assume that total mass of the heat-polymerizable liquid crystal mixture is 100%, the heat-polymerizable liquid crystal mixture comprises 35-73% of small molecule nematic liquid crystal, 10-20% of heat-polymerizable monomer, 12-20% of curing agent and 5-25% of chiral additive.
In an embodiment, the heat-polymerizable monomer includes a bisphenol F epoxy resin having the following molecular formula:
Figure US10059879-20180828-C00004
or a polyethylene glycol bisglycidyl ether having the following molecular formula:
Figure US10059879-20180828-C00005
In an embodiment, the curing agent includes 1,8-diamino-3,6-dioxaoctane having the following molecular formula:
Figure US10059879-20180828-C00006
or 4,4′-diaminodicyclohexylmethane having the following molecular formula:
Figure US10059879-20180828-C00007
In an embodiment, the chiral additive includes any one of the following substances:
Figure US10059879-20180828-C00008
With the liquid crystal composition of the embodiments of the present invention, a patterned phase delay film with high reflectance and transmittance can be obtained by UV-polymerizing and heat-polymerizing the liquid crystal composition. The preparation process is simple and the costs are low.
According to another aspect of the present invention, there is provided a patterned phase delay film which is prepared from the above-mentioned liquid crystal composition.
According to another aspect of the present invention, there is provided a preparation method for a patterned phase delay film, which comprises the following steps: injecting the above mentioned liquid crystal mixture into a liquid crystal cell; irradiating the liquid crystal cell covered with a photo mask with UV light to complete UV-polymerization; and heating the liquid crystal cell to complete heat-polymerization.
A person skilled in the art will appreciate that appropriate conditions for UV-polymerization and heat-polymerization may be selected in accordance with specific components of the liquid crystal composition and performance requirements on the obtained phase delay film.
In an embodiment, the condition for the UV-polymerization is wavelength of the UV light being 365 nm, intensity being 0.001-100 mW/cm2, and irradiation time being 5-240 min.
In an embodiment, the condition for the heat-polymerization is temperature ranging from 30 to 120° C. and heating time ranging from 20 to 60 min.
According to another aspect of the present invention, there is provided a display device which comprises the above mentioned patterned phase delay film.
Since the display device comprises the above mentioned patterned phase delay film, it can be used in 3D display with the advantages of simple preparation, low costs, and the like.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of the liquid crystal cell covered with a mask plate in a first embodiment of the present invention;
FIG. 2 is a schematic diagram of the region formed by UV radiation which reflects laevorotatory visible light band in the first embodiment of the present invention;
FIG. 3 is a schematic diagram of the region formed by heating which reflects dextrorotatory visible light band in the first embodiment of the present invention; and
FIG. 4 is a curve diagram of the transmittance of the patterned phase delay film formed in the first embodiment of the present invention in the range of wavelength of 350 nm-750 nm.
 DETAILED DESCRIPTION
To facilitate those skilled in the art to well understand the concept of the present invention, several embodiments of the present invention will be described in detail in conjunction with the drawings.
In one embodiment of the present invention, a liquid crystal composition is provided which comprises a laevorotatory photo-polymerizable liquid crystal mixture and a dextrorotatory heat-polymerizable liquid crystal mixture.
In another embodiment of the present invention, a liquid crystal composition is provided which comprises a dextrorotatory photo-polymerizable liquid crystal mixture and a laevorotatory heat-polymerizable liquid crystal mixture.
The photo-polymerizable liquid crystal mixture and heat-polymerizable liquid crystal mixture may comprise the previously mentioned various specific components. It should be understood that it is also possible to mix any other heat-polymerizable liquid crystal mixture and photo-polymerizable liquid crystal mixture in the prior art, as long as the optically rotatory directions of the two mixtures are opposite.
The photo-polymerizable liquid crystal mixture or heat-polymerizable liquid crystal mixture may comprise a small molecule nematic liquid crystal. In some embodiments, a liquid crystal temperature of the small molecule nematic liquid crystal ranges from −20° C. to 120° C., and an optical anisotropy Δn ranges from 0.19 to 0.21 (589 nm, 293K), e.g., SLC1717 (Shijiazhuang Yongshenghuaqing Liquid Crystal LTD.), MAT 10-1614 (Merck Corporation), ZBE-5371XX (JNC Corporation), and the like.
In one embodiment of the present invention, a patterned phase delay film is provided which is prepared from the above-mentioned liquid crystal composition. The preparation method comprises the following steps: injecting the above mentioned liquid crystal composition into a liquid crystal cell; irradiating the liquid crystal cell covered partially with a photo mask with UV light to complete the UV-polymerization; and heating the liquid crystal cell to complete the heat-polymerization so as to form the patterned phase delay film.
Specifically, the liquid crystal composition can be obtained by uniformly mixing the photo-polymerizable liquid crystal mixture and heat-polymerizable liquid crystal mixture by means of solvent evaporation or heat melting. The solvent evaporation and heat melting are conventional approaches. For the solvent evaporation, the solvent is usually selected from organic solvents, such as tetrahydrofuran, acetone, dichloromethane, or the like. For the heat melting, the liquid crystal composition can be heated to its clearing point temperature to carry out the melt mixing. The specific operation conditions will not be repeated here.
Then referring to FIG. 1, the liquid crystal composition is injected into the liquid crystal cell 2 on the glass substrate 1, and the photo mask 3 is placed on the liquid crystal cell 2. The photo mask 3 may be a photo shielding strip arranged at intervals. The liquid crystal cell 2 may be irradiated with UV light at a wavelength of 365 nm, under an irradiation intensity of 0.001-100 mW/cm2 for 5-240 min. In some embodiments, the irradiation intensity of the UV light is 0.1-15 mW/cm2 and the irradiation time is 10-100 min.
The concentration gradient of the photo-polymerizable monomer may be represented by a polymerization rate difference in the photo-polymerizable monomer polymerization. In the direction vertical to the polymer network (i.e. the direction vertical to the glass substrate 1 in the liquid crystal cell), the polymerization rate is faster at the side near the UV light, which causes the photo-polymerizable monomers away from the UV light and those at the place covered by the photo mask 3 to migrate to the side near the UV light. Most of the photo-polymerizable monomers may migrate to the light permeable region of the photo mask 3. The polymer network formed near the UV light is more intensive than that formed away from the UV light. That is, in the direction vertical to the polymer network (i.e. the direction vertical to the glass substrate 1 in the liquid crystal cell), the concentration gradient of the polymer network of photo-polymerizable monomers is formed. Moreover the photo-polymerizable monomers at the place covered by the photo mask 3 may migrate to the side near the UV light, so the concentration gradient of the polymer network of photo-polymerizable monomers is also formed in the horizontal direction of the liquid crystal cell.
Thus the photo-polymerizable liquid crystal monomers at the place of the liquid crystal cell 2 irradiated with the UV light are polymerized during the migration, and after the polymerization, a concentration gradient polymer network of photo-polymerizable monomers is formed at the place of the liquid crystal cell 2 irradiated with the UV light. The rotatory direction of the concentration gradient polymer network may be determined by the contents and optical rotation of the chiral substances in the system. So the system exhibits levorotation if the content of the laevorotatory substance is higher, and the network after polymerization is a laevorotatory network. If the content of the dextrorotatory substance is higher in the system, the system exhibits dextrorotation, and the network after polymerization is a dextrorotatory network.
Then the UV-polymerized liquid crystal cell is placed on a heating platform for heating, so that the heat-polymerizable monomers in the liquid crystal composition are polymerized. The temperature of the heating platform may be 30° C.-120° C., and the heat curing time may be 20-60 min. In some embodiments, the temperature of the heating platform may be 80° C.-100° C., and the heat curing time may be 40-50 min.
The polymerization of heat-polymerizable monomers takes place when the temperature reaches the heat initiation temperature. Pure UV light irradiation would not lead to the heat-polymerization. In addition, in the step of UV light irradiation, since the difference of the polymerization rates of the photo-polymerizable monomers may cause the photo-polymerizable monomers to move to the direction with the stronger UV light, a majority of the heat-polymerizable monomers will be passively migrated (in the opposite direction), and the concentration gradient of heat-polymerizable monomers may be also formed. The content of heat-polymerizable monomers is lower near the place where the UV light is stronger, while the content of heat-polymerizable monomers is higher at the place where the UV light is weaker and the place covered by the photo mask 3, so the most of the heat-polymerizable monomers are migrated to the place covered by the photo mask, and thus the concentration gradient of heat-polymerizable monomers is formed opposite to the concentration gradient of photo-polymerizable monomers. That is, the concentration gradient of heat-polymerizable monomers is also formed in both the horizontal direction and vertical direction of the liquid crystal cell. During the heating, the concentration gradient of the polymer network of heat-polymerizable monomers is also formed in both the horizontal direction and vertical direction of the liquid crystal cell. Similarly, as the rotatory direction of the concentration gradient polymer network is determined by the contents and optical rotation of the chiral substances in the system, the system exhibits levorotation if the content of the laevorotatory substance is higher and the network after polymerization is a laevorotatory network, and if the content of the dextrorotatory substance is higher, the system exhibits dextrorotation, and the network after polymerization is a dextrorotatory network.
In addition, the heat-polymerizable monomers remained at the exposed place of the photo mask (i.e. the irradiated place of the photo mask) are polymerized upon heating. But the heat-polymerizable monomers remained at the exposed place of the photo mask (with lower contents) are not sufficient to change the optical rotation of the polymer network of photo-polymerizable monomers which has higher contents. After the polymerization, the heat-polymerizable monomers function to further stabilize the laevorotatory polymer network which is formed previously from the photo-polymerizable monomers. As shown in FIG. 3, the patterned phase delay film may be finally formed which may reflect laevorotatory polarized light and dextrorotatory polarized light at different positions. The laevorotatory and dextrorotatory polarization states may be separately distributed at intervals in accordance with the shape of the photo mask, that is, linear polarized lights of the same polarization state emitted from the adjacent pixel lines of the display panel may be converted into laevorotatory circular polarized lights and dextrorotatory circular polarized lights respectively.
Moreover the concentration gradients of polymer networks may be formed in the different regions (i.e. the covered region and the exposed region of the mask), i.e., helical pitch gradients of a cholesteric liquid crystal composite system.
The helical pitch gradients of the cholesteric liquid crystal composite system correspond to the selective reflection bandwidth range. The corresponding relation may comply with the Bragg reflection formula: Δλ=Δn×Δp, wherein Δλ, is the selective reflection bandwidth, Δn is the liquid crystal birefringence, and Δp is the helical pitch gradient of the liquid crystal composite system. Thus the different regions may reflect the lights of the corresponding bandwidth ranges.
In one embodiment of the present invention, a patterned phase delay film is provided which may be prepared from the liquid crystal composition according to the embodiments of the present invention by the above-mentioned preparation method. The patterned phase delay film may have the advantages of simple preparation process and low cost.
In one embodiment of the present invention, a display device is provided which comprises the above-mentioned patterned phase delay film. Since the display device is configured with the above-mentioned patterned phase delay film, it can be used in 3D display.
Embodiment 1
The present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture. The amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1.
The laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 (Shijiazhuang Yongshenghuaqing Liquid Crystal LTD.) as the small molecule nematic liquid crystal, the photo-polymerizable liquid crystal monomer having the molecular formula of:
Figure US10059879-20180828-C00009
the UV-absorbing dye having the molecular formula of:
Figure US10059879-20180828-C00010
the chiral additive having the molecular formula of:
Figure US10059879-20180828-C00011
and
the photoinitiator having the molecular formula of:
Figure US10059879-20180828-C00012
The dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, a bisphenol F epoxy resin as the heat-polymerizable monomers having the following molecular formula:
Figure US10059879-20180828-C00013
4,4′-diaminodicyclohexylmethane as the curing agent having the following molecular formula:
Figure US10059879-20180828-C00014
and
the chiral additive having the following molecular formula:
Figure US10059879-20180828-C00015
The laevorotatory photo-polymerizable liquid crystal mixture and dextrorotatory heat-polymerizable liquid crystal mixture may be mixed into a uniform mixture according to the mixing mass ratio of Table 1 by means of solvent evaporation, thereby obtaining a liquid crystal composition, wherein the total mass of the photo-polymerizable liquid crystal mixture is 1 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 1 gram. The mass of each component in the photo-polymerizable liquid crystal mixture may be calculated according to the mass percentage in Table 1, and the corresponding mass of each component is weighed. The respective components may be placed into a 5 ml glass bottle. Acetone may be added slowly, dropwise into the glass bottle until the components are completely dissolved. Subsequently, the glass bottle may be placed on a heating platform of 40° C. for 5-6 hours until the solvent evaporates completely, and the formulation of the photo-polymerizable liquid crystal mixture is finished. Then, the heat-polymerizable liquid crystal mixture may be formulated according to the same process.
As shown in FIG. 1, the above-mentioned liquid crystal mixtures may be injected into the liquid crystal cell 2 on the glass substrate 1, and the photo mask 3 may be placed on the prepared liquid crystal cell 2. The pattern of the photo mask 3 may be photo shielding strips arranged at intervals.
The liquid crystal cell 2 may be irradiated with UV light at a wavelength of 365 nm, under an irradiation intensity of 1.4 mW/cm2, for 25 minutes.
As shown in FIG. 2, the polymerization network of the photo-polymerizable monomers may reflect laevorotatory visible light bands, and hence the region on the liquid crystal layer corresponding to the light permeable region of the photo mask 3 may reflect the laevorotatory visible light bands.
The UV-polymerized liquid crystal cell is placed on a heating platform (for heating), so that the heat-polymerizable monomers in the liquid crystal mixtures are polymerized. The temperature of the heating platform may be 80° C., and the heat curing time may be 45 minutes. The polymerization network obtained by curing the heat-polymerizable monomers may form a region which may reflect dextrorotatory visible light bands.
As shown in FIG. 3, the patterned phase delay film is finally formed which may reflect the laevorotatory polarized light and dextrorotatory polarized light at different positions. The laevorotatory and dextrorotatory polarization films are separated from each other and distributed at intervals in accordance with the shape of the photo mask, so that the polarization films can convert the linear polarized lights of the same polarization state emitted from the adjacent pixel lines of the display panel into the laevorotatory circular polarized lights and dextrorotatory circular polarized lights respectively.
Moreover, the concentration gradients of the polymer networks are formed at different regions (the covered region and exposed region of the mask), i.e., helical pitch gradients of a cholesteric liquid crystal composite system.
The film obtained by the two-step polymerization process is subjected to a spectrum test, and the result is as shown in FIG. 4. Curve 1 is the spectrum curve of the portion obtained by UV-polymerization, which may implement the selective reflection of laevorotatory light in the waveband range of 350 nm-750 nm. Curve 2 is the spectrum curve of the portion obtained by heat-polymerization, which may implement the selective reflection of dextrorotatory light in the waveband range of 350 nm-750 nm.
Embodiment 2
The present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture. The amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1, wherein the total mass of the photo-polymerizable liquid crystal mixture is 1.43 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 0.57 gram.
The laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the photo-polymerizable liquid crystal monomers having the molecular formula of:
Figure US10059879-20180828-C00016
the UV-absorbing dye having the molecular formula of:
Figure US10059879-20180828-C00017
the chiral additive having the molecular formula of:
Figure US10059879-20180828-C00018
and
the photoinitiator having the molecular formula of:
Figure US10059879-20180828-C00019
The dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 (Shijiazhuang Yongshenghuaqing Liquid Crystal LTD.) as the small molecule nematic liquid crystal, a bisphenol F epoxy resin as the heat-polymerizable monomer having the following molecular formula:
Figure US10059879-20180828-C00020
4,4′-diaminodicyclohexylmethane as the curing agent having the following molecular formula:
Figure US10059879-20180828-C00021
and
a chiral additive having the following molecular formula:
Figure US10059879-20180828-C00022
From such the liquid crystal composition, the patterned phase-delay film may be prepared according to the same preparation process as in the first embodiment with the differences that the wavelength of the UV irradiation is 365 nm, the UV light intensity is 100 mW/cm2, the duration of UV irradiation is 5 minutes, the temperature of the heating platform is 40° C., and the heat curing time is 50 minutes.
The spectrogram of the patterned phase-delay film obtained after the two-step polymerization is similar to FIG. 4.
Embodiment 3
The present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture. The amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1, wherein the total mass of the photo-polymerizable liquid crystal mixture is 0.67 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 1.33 gram.
The laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the photo-polymerizable liquid crystal monomers having the molecular formula of:
Figure US10059879-20180828-C00023
the UV-absorbing dye having the molecular formula of:
Figure US10059879-20180828-C00024
the chiral additive having the molecular formula of:
Figure US10059879-20180828-C00025
and
the photoinitiator having the molecular formula of:
Figure US10059879-20180828-C00026
The dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, a bisphenol F epoxy resin as the heat-polymerizable monomer having the following molecular formula:
Figure US10059879-20180828-C00027
4,4′-diaminodicyclohexylmethane as the curing agent having the following molecular formula:
Figure US10059879-20180828-C00028
and
the chiral additive having the following molecular formula:
Figure US10059879-20180828-C00029
From such the liquid crystal composition, the patterned phase delay film may be prepared according to the same preparation process as in the first embodiment with the differences that the wavelength of the UV irradiation is 365 nm, the UV light intensity is 30 mW/cm2, the duration of UV irradiation is 90 minutes, the temperature of the heating platform is 50° C., and the heat curing time is 40 minutes.
The spectrogram of the patterned phase-delay film obtained after the two-step polymerization is similar to FIG. 4.
Embodiment 4
The present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture. The amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1, wherein the total mass of the photo-polymerizable liquid crystal mixture is 0.5 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 1.5 gram.
The laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the photo-polymerizable liquid crystal monomers having the molecular formula of:
Figure US10059879-20180828-C00030
the UV-absorbing dye having the molecular formula of:
Figure US10059879-20180828-C00031
the chiral additive having the molecular formula of:
Figure US10059879-20180828-C00032
and
the photoinitiator having the molecular formula of:
Figure US10059879-20180828-C00033
The dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystals, the polyethylene glycol bisglycidyl ether as the heat-polymerizable monomer having the following molecular formula:
Figure US10059879-20180828-C00034
1,8-diamino-3,6-dioxaoctane as the curing agent having the following molecular formula:
Figure US10059879-20180828-C00035
and
the chiral additive having the following molecular formula:
Figure US10059879-20180828-C00036
From such the liquid crystal composition, the patterned phase delay film may be prepared according to the same preparation process as in the first embodiment with the differences that the wavelength of the UV irradiation is 365 nm, the UV light intensity is 60 mW/cm2, the duration of UV irradiation is 60 minutes, the temperature of the heating platform is 70° C., and the heat curing time is 35 minutes.
The spectrogram of the patterned phase-delay film obtained after the two-step polymerization is similar to FIG. 4.
Embodiment 5
The present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture. The amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1, wherein the total mass of the photo-polymerizable liquid crystal mixture is 1.11 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 0.89 gram.
The laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystals, the photo-polymerizable liquid crystal monomers having the molecular formula of:
Figure US10059879-20180828-C00037
the UV-absorbing dye having the molecular formula of:
Figure US10059879-20180828-C00038
the chiral additive having the molecular formula of:
Figure US10059879-20180828-C00039
and
the photoinitiator having the molecular formula of:
Figure US10059879-20180828-C00040
The dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the polyethylene glycol bisglycidyl ether as the heat-polymerizable monomer having the following molecular formula:
Figure US10059879-20180828-C00041
1,8-diamino-3,6-dioxaoctane as the curing agent having the following molecular formula:
Figure US10059879-20180828-C00042
and
the chiral additive having the following molecular formula:
Figure US10059879-20180828-C00043
From such the liquid crystal composition, the patterned phase delay film may be prepared according to the same preparation process as in the first embodiment with the differences that the wavelength of the UV irradiation is 365 nm, the UV light intensity is 0.001 mW/cm2, the duration of UV irradiation is 240 minutes, the temperature of the heating platform is 30° C., and the heat curing time is 60 minutes.
The spectrogram of the patterned phase-delay film obtained after the the two-step polymerization is similar to FIG. 4.
Embodiment 6
The present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture. The amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1, wherein the total mass of the photo-polymerizable liquid crystal mixture is 0.57 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 1.43 gram.
The laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the photo-polymerizable liquid crystal monomers having the molecular formula of:
Figure US10059879-20180828-C00044
the UV-absorbing dye having the molecular formula of:
Figure US10059879-20180828-C00045
the chiral additive having the molecular formula of:
Figure US10059879-20180828-C00046
and
the photoinitiator having the molecular formula of:
Figure US10059879-20180828-C00047
The dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the polyethylene glycol bisglycidyl ether as the heat-polymerizable monomers having the following molecular formula:
Figure US10059879-20180828-C00048
1,8-diamino-3,6-dioxaoctane as the curing agent having the following molecular formula:
Figure US10059879-20180828-C00049
and
the chiral additive having the following molecular formula:
Figure US10059879-20180828-C00050
From such the liquid crystal composition, the patterned phase delay film may be prepared according to the same preparation process as in the first embodiment with the differences that the wavelength of the UV irradiation is 365 nm, the UV light intensity is 80 mW/cm2, the duration of UV irradiation is 30 minutes, the temperature of the heating platform is 100° C., and the heat curing time is 25 minutes.
The spectrogram of the patterned phase-delay film obtained after the two-step polymerization is similar to FIG. 4.
Table 1 shows the mass ratios of the photo-polymerizable mix liquid crystals and heat-polymerizable mix liquid crystals as well as the mixing ratios in the above embodiments.
TABLE 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7
Photo-polymerizable
mix liquid crystal
Small molecule nematic 28 69.5 42 60 53 35 46
liquid crystal (%)
Photo-polymerizable 40 27.9 28 26 15 35 24
crystal monomer (%)
UV-absorbing dye (%) 2 2 15 10 8 5 5
Chiral additive (%) 25 0.1 12 3 20 23 23
Photoinitiator (%) 5 0.5 3 1 4 2 2
Heat-polymerizable
mix liquid crystal
Small molecule nematic 35 73 45 55 65 70 49
liquid crystal (%)
Heat-polymerizable 20 10 15 18 12 11 17
monomer (%)
Curing agent (%) 20 12 16 17 18 13 16
Chiral additive (%) 25 5 24 10 5 6 18
Mass ratios of 1:1 1:0.4 1:2 1:3 1:0.8 1:2.5 1:1.5
photo-polymerizable
mix liquid crystals to
heat-polymerizable mix
liquid crystals
It should be understood that the above embodiments disclosed herein are exemplary only and not limiting the scope of this disclosure. Without departing from the spirit and scope of this invention, other modifications, equivalents, or improvements to the disclosed embodiments are obvious to those skilled in the art and are intended to be encompassed within the scope of the present disclosure.

Claims (16)

What is claimed is:
1. A method for preparing a patterned phase delay film comprising the steps of:
injecting a liquid crystal composition into a liquid crystal cell;
irradiating the liquid crystal cell partially covered with a photo mask with UV light to complete UV-polymerization; and
heating the liquid crystal cell to complete heat-polymerization,
wherein the liquid crystal composition comprises a photo-polymerizable liquid crystal mixture and a heat-polymerizable liquid crystal mixture, wherein the photo-polymerizable liquid crystal mixture and heat-polymerizable liquid crystal mixture have opposite rotatory directions,
wherein the photo-polymerizable liquid crystal mixture comprises a small molecule nematic liquid crystal, a photo-polymerizable monomer, a UV-absorbing dye, a chiral additive, and a photoinitiator; and
wherein the heat-polymerizable liquid crystal mixture comprises a small molecule nematic liquid crystal, a heat-polymerizable monomer, a curing agent, and a chiral additive.
2. The method according to claim 1, wherein a condition for the UV-polymerization is UV light intensity being 0.001-100 mW/cm2 and irradiation time being 5-240 min.
3. The method according to claim 1, wherein a condition for the heat-polymerization is temperature being 30-120° C. and heating time being 20-60 min.
4. The method of claim 1, wherein the liquid crystal composition has a mass ratio of the photo-polymerizable liquid crystal mixture to the heat-polymerizable liquid crystal mixture of 1: (0.4-3).
5. The method of claim 1, wherein the photo-polymerizable liquid crystal mixture comprises, by mass percentage, 28-69.5% of the small molecule nematic liquid crystal, 15-40% of the photo-polymerizable monomer, 2-15% of the UV-absorbing dye, 0.1-25% of chiral additive, and 0.5-5% of photoinitiator.
6. The method of claim 1, wherein the photo-polymerizable monomer is selected from the group consisting of:
Figure US10059879-20180828-C00051
7. The method of claim 1, wherein the UV-absorbing dye comprises:
Figure US10059879-20180828-C00052
8. The method of claim 1, wherein the photoinitiator comprises:
Figure US10059879-20180828-C00053
9. The method of claim 1, wherein the heat-polymerizable liquid crystal mixture comprises, by mass percentage, 35-73% of the small molecule nematic liquid crystal, 10-20% of the heat-polymerizable monomer, 12-20% of the curing agent and 5-25% of the chiral additive.
10. The method of claim 1, wherein the heat-polymerizable monomer comprises
a bisphenol F epoxy resin which has the following molecular formula:
Figure US10059879-20180828-C00054
or
a polyethylene glycol bisglycidyl ether which has the following molecular formula:
Figure US10059879-20180828-C00055
11. The method of claim 1, wherein the curing agent comprises:
1,8-diamino-3,6-dioxaoctane which has the following molecular formula:
Figure US10059879-20180828-C00056
or
4,4′-diaminodicyclohexylmethane which has the following molecular formula:
Figure US10059879-20180828-C00057
12. The method of claim 1, wherein the chiral additive is selected from the group consisting of
Figure US10059879-20180828-C00058
13. A display device comprising a patterned phase-delay film,
wherein the patterned phase delay film is prepared from a liquid crystal composition, and
wherein the liquid crystal composition comprises a photo-polymerizable liquid crystal mixture and a heat-polymerizable liquid crystal mixture, wherein the photo-polymerizable liquid crystal mixture and heat-polymerizable liquid crystal mixture have opposite rotatory directions,
wherein the photo-polymerizable liquid crystal mixture comprises a small molecule nematic liquid crystal, a photo-polymerizable monomer, a UV-absorbing dye, a chiral additive and a photoinitiator; and
wherein the heat-polymerizable liquid crystal mixture comprises a small molecule nematic liquid crystal, a heat-polymerizable monomer, a curing agent and a chiral additive.
14. The display device according to claim 13, wherein the liquid crystal composition has a mass ratio of the photo-polymerizable liquid crystal mixture to the heat-polymerizable liquid crystal mixture of 1: (0.4-3).
15. The display device according to claim 13, wherein the photo-polymerizable liquid crystal mixture comprises, by mass percentage, 28-69.5% of the small molecule nematic liquid crystal, 15-40% of the photo-polymerizable monomer, 2-15% of the UV-absorbing dye, 0.1-25% of the chiral additive and 0.5-5% of the photoinitiator.
16. The display device according to claim 13, wherein the heat-polymerizable liquid crystal mixture comprises, by mass percentage, 35-73% of the small molecule nematic liquid crystal, 10-20% of the heat-polymerizable monomer, 12-20% of the curing agent and 5-25% of the chiral additive.
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Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104403677B (en) 2014-12-15 2016-08-24 京东方科技集团股份有限公司 A kind of liquid crystal compound, patterned phase retardation membrane and preparation method, display device
KR102380155B1 (en) * 2015-03-25 2022-03-29 삼성디스플레이 주식회사 Optical unit and organic light emitting diode display comprising the same
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Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1295929A2 (en) 2001-09-25 2003-03-26 MERCK PATENT GmbH Anisotropic polymer film
JP2003147363A (en) * 2001-11-19 2003-05-21 Minolta Co Ltd Method for preparing chiral nematic liquid crystal compositions and liquid crystal display element
US20030104144A1 (en) * 2001-09-25 2003-06-05 Merck Patent Gmbh Anisotrpic polymer film
JP2005113131A (en) 2003-09-19 2005-04-28 Chisso Corp Photopolymerizable liquid crystal composition and its polymer or polymer composition and optically anisotropic membrane
US20050151906A1 (en) 2002-04-26 2005-07-14 Hiroyuki Yoshimi Method for producing birefringent film
CN1841157A (en) 2005-03-29 2006-10-04 大日本印刷株式会社 Process for producing optical element
CN101225308A (en) 2007-09-17 2008-07-23 北京科技大学 Method for preparing polymer dispersion liquid crystal material by ultraviolet-heating step-polymerization process
US20110086185A1 (en) * 2009-10-13 2011-04-14 Chisso Corporation Polymerizable liquid crystal compound and its polymer
CN102071031A (en) 2010-12-24 2011-05-25 北京科技大学 Method for preparing epoxy-based polymer dispersed liquid crystal film material
US20120050631A1 (en) * 2004-09-24 2012-03-01 Sharp Kabushiki Kaisha Liquid crystal display device
CN102388013A (en) 2009-05-19 2012-03-21 Jnc株式会社 Chlorobenzene derivative, optically isotropic liquid crystal medium, and optical element
CN102634348A (en) 2012-03-21 2012-08-15 广东东邦科技有限公司 Mixed liquid crystal solution, liquid crystal visual angle enlarging film, preparation method of liquid crystal visual angle enlarging film and liquid crystal display device
CN102778718A (en) * 2012-07-05 2012-11-14 北京科技大学 Method for preparing broadband reflection liquid crystal polarizing film with high performance
JP2013037356A (en) 2011-07-14 2013-02-21 Mitsubishi Chemicals Corp Coloring liquid for color filter, colored resin composition for color filter, color filter, liquid crystal display device and organic el display device
CN103275736A (en) 2013-06-05 2013-09-04 浙江星星光学材料有限公司 Preparation method of polymer-stabilized liquid crystal thin film material with wide wave reflection
CN104403677A (en) 2014-12-15 2015-03-11 京东方科技集团股份有限公司 Liquid crystal mixture, patterning phase delay membrane and preparation method thereof, as well as display device

Patent Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1295929A2 (en) 2001-09-25 2003-03-26 MERCK PATENT GmbH Anisotropic polymer film
US20030104144A1 (en) * 2001-09-25 2003-06-05 Merck Patent Gmbh Anisotrpic polymer film
JP2003147363A (en) * 2001-11-19 2003-05-21 Minolta Co Ltd Method for preparing chiral nematic liquid crystal compositions and liquid crystal display element
US20050151906A1 (en) 2002-04-26 2005-07-14 Hiroyuki Yoshimi Method for producing birefringent film
CN1650198A (en) 2002-04-26 2005-08-03 日东电工株式会社 Manufacturing method of double refraction film
JP2005113131A (en) 2003-09-19 2005-04-28 Chisso Corp Photopolymerizable liquid crystal composition and its polymer or polymer composition and optically anisotropic membrane
US20120050631A1 (en) * 2004-09-24 2012-03-01 Sharp Kabushiki Kaisha Liquid crystal display device
CN1841157A (en) 2005-03-29 2006-10-04 大日本印刷株式会社 Process for producing optical element
US20060222783A1 (en) 2005-03-29 2006-10-05 Dai Nippon Printing Co., Ltd. Process for producing optical element
CN101225308A (en) 2007-09-17 2008-07-23 北京科技大学 Method for preparing polymer dispersion liquid crystal material by ultraviolet-heating step-polymerization process
US20120099039A1 (en) 2009-05-19 2012-04-26 Jnc Petrochemical Corporation Chlorobenzene derivative, optically isotropic liquid crystal medium, and optical device
CN102388013A (en) 2009-05-19 2012-03-21 Jnc株式会社 Chlorobenzene derivative, optically isotropic liquid crystal medium, and optical element
US20110086185A1 (en) * 2009-10-13 2011-04-14 Chisso Corporation Polymerizable liquid crystal compound and its polymer
CN102071031A (en) 2010-12-24 2011-05-25 北京科技大学 Method for preparing epoxy-based polymer dispersed liquid crystal film material
JP2013037356A (en) 2011-07-14 2013-02-21 Mitsubishi Chemicals Corp Coloring liquid for color filter, colored resin composition for color filter, color filter, liquid crystal display device and organic el display device
CN102634348A (en) 2012-03-21 2012-08-15 广东东邦科技有限公司 Mixed liquid crystal solution, liquid crystal visual angle enlarging film, preparation method of liquid crystal visual angle enlarging film and liquid crystal display device
CN102778718A (en) * 2012-07-05 2012-11-14 北京科技大学 Method for preparing broadband reflection liquid crystal polarizing film with high performance
CN103275736A (en) 2013-06-05 2013-09-04 浙江星星光学材料有限公司 Preparation method of polymer-stabilized liquid crystal thin film material with wide wave reflection
CN104403677A (en) 2014-12-15 2015-03-11 京东方科技集团股份有限公司 Liquid crystal mixture, patterning phase delay membrane and preparation method thereof, as well as display device
US20160355733A1 (en) 2014-12-15 2016-12-08 Beijing Boe Display Technology Co., Ltd. Liquid crystal composition, patterned phase delay film and preparation method thereof, and display device

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
English Translation of CN101225308. *
English Translation of CN102071031. *
English Translation of CN102778718. *
English Translation of JP2003147363. *
Guo et al., "Bandwidth-controllable reflective cholesteric gels from photo- and thermally-induced processes", Mar. 2010, Liquid Crystals, vol. 37, No. 3, 311-316. *
International Search Report (ISR) from PCT/CN2015/081730 dated Aug. 26, 2015.
Office Action from corresponding Chinese Patent Application No. 201410779593.6 dated Dec. 28, 2015.
Written Opinion of the International Searching Authority from PCT/CN2015/081730 dated Aug. 28, 2015.

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